The present invention relates to {circle around (1)} a purifying process of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide. The present invention also relates to {circle around (2)} a tetrakis(fluoroaryl)boratexe2x80xa2ether complex, which is useful as, for example, a co-catalyst of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, a photopolymeric catalyst for silicone, a cationic polymerization initiator used in the polymerization of a functional polymer or monomer with photochemical activation or irradiation of electron beams, and an intermediate for producing tetrakis(pentafluorophenyl)borate derivatives of various kinds, and to a process of producing the same; and to {circle around (3)} a process of producing a tetrakis(fluoroaryl)borate derivative. Further, the present invention relates to {circle around (4)} a tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex useful as an intermediate for producing the tetrakis(fluoroaryl)borate derivative and a process of producing the same, and to {circle around (5)} a process of producing tetrakis(fluoroaryl)borate.
A tetrakis(fluoroaryl)borate derivative is an useful compound as, for example, a co-catalyst for promoting the activity of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, or a photopolymeric catalyst for silicone. Also, tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is an useful compound as an intermediate for producing the tetrakis(fluoroaryl)borate derivative. Recently, the metallocene catalyst has been receiving considerable attention as a polyolefin polymeric catalyst.
A producing process of tetrakis (pentafluorophenyl)boratexe2x80xa2magensium bromide, which is a kind of tetrakis(fluoroaryl)boratexe2x80xa2magensium halide, from bromopentafluorobenzene through the Grignard reaction is disclosed in, for example, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980).
Also, in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981), a process of synthesizing tetrakis (pentafluorophenyl)boratexe2x80xa2lithium from pentafluorobenzene using an organic lithium compound and boron halide first, and thence reacting the resulting compound with N,N-dimethylanilinexe2x80xa2hydrochloride is disclosed as a process of producing a tetrakis (pentafluorophenyl)borate derivative, which is a kind of the tetrakis(fluoroaryl)borate derivative.
Further, a process of producing the tetrakis (pentafluorophenyl)borate derivative by reacting tetrakis (pentafluorophenyl) boratexe2x80xa2magnesium bromide with N,N-dimethylanilinexe2x80xa2hydrochloride is disclosed in U.S. Pat. No. 5,473,036.
However, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) neither discloses nor implies the separation/removal of magnesium halide, a by-product produced with tetrakis (pentafluorophenyl)boratexe2x80xa2magnesium bromide, from the reaction series. If the tetrakis(pentafluorophenyl) borate derivative is produced from tetrakis (pentafluorophenyl)boratexe2x80xa2magnesium bromide containing magnesium halide as impurities, and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably. The process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) is a producing process of tetrakis(pentafluorophenyl) boratexe2x80xa2magnesium bromide containing magnesium halide as impurities. Thus, tetrakis(pentafluorophenyl)boratexe2x80xa2magnesium bromide obtained through this process can not be used as an adequate intermediate for producing the tetrakis(pentafluorophenyl)borate derivative.
If typical alkali treatment is applied to tetrakis (pentafluorophenyl)boratexe2x80xa2magnesium bromide to remove magnesium halide from tetrakis(pentafluorophenyl) boratexe2x80xa2magnesium bromide obtained by the process disclosed in the above publication, magnesium hydroxide is produced. Since magnesium hydroxide turns a post-treatment solution into gel, the solution can not be filtered. In other words, since magnesium halide can not be removed by the typical alkali treatment, it is difficult to separate tetrakis(pentafluorophenyl) boratexe2x80xa2magnesium bromide obtained in the above process, or to obtain a highly-pure tetrakis(fluoroaryl)borate compound after the treatment.
Thus, there has been an increasing demand for a purifying process for separating/removing impurities, such as magnesium halide, from tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide readily and efficiently.
On the other hand, the process disclosed in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the following problems:
(1) since the reaction series must be kept at xe2x88x9265xc2x0 C. or below, not only special equipment is required, but also the cooling cost is high;
(2) the process demands an expensive organic lithium compound (t-butyl lithium), which is a dangerous compound because it may ignite when reacted with water and the like;
(3) the process also demands expensive boron halide (boron trichloride), which is very difficult to handle because it is in the gaseous state and corrosive. Thus, the process disclosed in the above publication can not be readily adopted for industrial use.
In the process disclosed in U.S. Pat. No. 5,473,036, magnesium hydroxide is produced as a by-product with the object product, that is, the tetrakis (pentafluorophenyl)borate derivative. Since magnesium hydroxide turns a post-treatment solution into gel, it is difficult to separate (isolate) the tetrakis (pentafluorophenyl)borate derivative from the solution. Thus, there arises a problem that the tetrakis (pentafluorophenyl)borate derivative can not be produced efficiently.
In other words, the conventional producing processes have a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently. Hence, there has been an increasing demand for a process of producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently.
Therefore, it is a first object of the present invention to provide a purifying process of separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide readily and efficiently. Also, it is a second object of the present invention to provide a process of efficiently producing an inexpensive and highly-pure tetrakis (fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone.
A process of producing tetrakis (pentafluorophenyl)borate, which is useful as an intermediate for producing the tetrakis (pentafluorophenyl)borate derivatives of various kinds, has been known.
, a process of obtaining tetrakis (pentafluorophenyl)borate.lithium by reacting pentafluorophenyl lithium, which is produced by reacting pentafluorophenyl bromide with butyl lithium at xe2x88x9278xc2x0 C. in dry pentane, with tris(pentafluorophenyl)borate at xe2x88x9278xc2x0 C. in dry pentane is disclosed in p245, J. Organometallic. Chem., 2, (1964).
Also, aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) discloses a process of preparing tetrakis (pentafluorophenyl)boratexe2x80xa2lithium used in the producing process of N,N-dimethyl aniliniumxe2x80xa2tetrakis (pentafluorophenyl)borate from N,N-dimethylanilinexe2x80xa2hydrochloride as follows.
That is, the above publication discloses a process of preparing, in which pentafluorophenyl lithium is produced initially by reacting pentafluorophenyl bromide with t-butyl lithium at xe2x88x9265xc2x0 C. in dry diethyl ether, and then tetrakis (pentafluorophenyl) boratexe2x80xa2lithium is prepared by reacting the resulting pentafluorophenyl lithium with boron trichloride at xe2x88x9265xc2x0 C. to xe2x88x9255xc2x0 C. in dry pentane.
However, the process disclosed in p245, J. Organometallic. Chem., 2, (1964) has a problem that the yield of tetrakis(pentafluorophenyl)boratexe2x80xa2lithium is low (43%). Also, since the process disclosed in aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the above-explained problem, it can not be readily applied to industrial use.
On the other hand, aforementioned Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) discloses a process of obtaining the tetrakis(pentafluorophenyl)borate derivative by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoridexe2x80xa2diethyl ether complex.
Also, aforementioned U.S. Pat. No. 5,473,035 discloses a process of obtaining tetrakis (pentafluorophenyl) boratexe2x80xa2magnesium bromide by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoridexe2x80xa2diethyl ether complex, and a process of obtaining N,N-dimethyl aniliniumxe2x80xa2tetrakis (pentafluorophenyl)borate by reacting tetrakis (pentafluorophenyl)boratexe2x80xa2magnesium bromide with an aqueous solution of N,N-dimethylanilinexe2x80xa2hydrochloride.
However, in the process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), magnesium halide, such as magnesium bromide fluoride (MgBrF), produced as a by-product with tetrakis(pentafluorophenyl)boratexe2x80xa2magnesium bromide, is not separated/removed from the reaction series and remains therein as impurities. Thus, as previously mentioned, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl) boratexe2x80xa2magnesium bromide containing magnesium halide as impurities and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably.
Further, in the processes disclosed in U.S. Pat. No. 398,236 and Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), resulting tetrakis (pentafluorophenyl)boratexe2x80xa2magnesium bromide is colored with a coloring component derived from the Grignard reaction. Thus, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl) boratexe2x80xa2magnesium bromide obtained in either of the above processes, there arises a problem that the coloring component remains in the tetrakis(pentafluorophenyl) borate derivative (the tetrakis(pentafluorophenyl)borate derivative is colored).
The process of producing tetrakis(pentafluorophenyl)borate derivative disclosed in U.S. Pat. No. 5,473,036 also has the following problem. That is, in the above process, a post-treatment solution is turned into gel by magnesium hydroxide produced as a by-product. Thus, it is difficult to filter the solution and isolate the tetrakis(pentafluorophenyl)borate derivative from the solution. Also, to isolate the tetrakis (pentafluorophenyl)borate derivative in the above process, a crude product must be crystallized again using a chlorine solvent, such as chloroform and dichloroethane.
As has been explained, since tetrakis(fluoroaryl) boratexe2x80xa2magnesium bromide obtained by the conventional processes contains the by-product salts and coloring component as impurities, it can not be used as an adequate intermediate for producing the tetrakis (fluoroaryl)borate derivative. Hence, there has been an increasing demand for a tetrakis(fluoroaryl)borate derivative which can be used as a suitable intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
It is therefore a third object of the present invention to provide a tetrakis(fluoroaryl)borate.ether complex as a new material which can be used suitably as a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds and the like, and a producing process of the same.
Also, the conventional producing processes of the tetrakis(fluoroaryl)borate derivative from tetrakis(fluoroaryl)borate prepared using an organic lithium compound or a Grignard reagent has a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently.
It is therefore a fourth object of the present invention to provide a process of producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently. Also, it is a fifth object of the present invention to provide a process of producing highly-pure tetrakis (fluoroaryl)borate. Further, it is a sixth object of the present invention to provide a tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex as a new material, which is useful not only as an intermediate for producing the tetrakis(fluoroaryl)borate derivative, but also as a co-catalyst of the metallocene catalyst (polymeric catalyst) used in the cationic complex polymerization reaction, and a process of producing the same. Furthermore, it is a seventh object of the present invention to provide a process of producing an inexpensive tetrakis(fluoroaryl)borate derivative from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex efficiently.
To fulfill the first and second objects, the inventors of the present invention conducted an assiduous study on the process of purifying tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide and the process of producing the tetrakis(fluoroaryl)borate derivative. In due course, the inventors achieved the present invention when they discovered that:
the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide by treating tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide with, for example, alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid; and
an inexpensive and highly-pure tetrakis (fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone, can be produced efficiently by reacting a tetrakis(fluoroaryl)borate compound obtained through the above purifying process with a compound generating monovalent cationic compounds.
In other words, to fulfill the above objects, a process of purifying tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide of the present invention is characterized by treating tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide expressed by General Formula (1): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R6-R10 represents a fluorine atom, X represents a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3, with:
{circle around (1)} alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid;
{circle around (2)} an acid;
{circle around (3)} an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or
{circle around (4)} an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid.
According to the above process, magnesium halide, such as magnesium bromide fluoride, produced as a by-product during the producing process of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide through the Grignard reaction can be turned into water-soluble or water-insoluble magnesium salts (that is, in the state of salts other than magnesium hydroxide). Thus, the salts can be readily and efficiently separated/removed from tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide through oil-water separation, filtration or the like. In short, the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide.
When tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide is treated with the purifying process {circle around (1)}, {circle around (3)} or {circle around (4)}, alkali metal salts and/or alkaline earth metal salts of tetrakis(fluoroaryl)borate can be obtained. When tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is treated with the purifying process {circle around (2)}, hydrogen compound of tetrakis(fluoroaryl)borate can be obtained.
A process of producing a tetrakis(fluoroaryl)borate derivative of the present invention relates to a process of producing a tetrakis(fluoroaryl)borate derivative expressed by General Formula (2): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R6-R10 represents a fluorine atom, Z+ represents a monovalent cation seed, and n represents 2 or 3, and is characterized by reacting a tetrakis(fluoroaryl)borate compound obtained by any of the purifying processes {circle around (1)}-{circle around (4)} with a compound generating monovalent cation compounds.
According to the above process, an inexpensive tetrakis(fluoroaryl)borate derivative can be produced efficiently from the tetrakis(fluoroaryl)borate compound obtained through any of the above purifying processes, namely, alkali metal salts, alkaline earth metal salts, and hydrogen compounds of tetrakis(fluoroaryl)borate. The resulting tetrakis(fluoroaryl)borate derivative does not contain the impurities, such as magnesium halide, and therefore is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst used in the cationic complex polymerization reaction or photopolymeric catalyst for silicone.
Also, to fulfill the third object, the inventors of the present invention conducted an assiduous study on the tetrakis(fluoroaryl)boratexe2x80xa2ether complex and the process of producing the same. In due course, the inventors discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)boratexe2x80xa2ether complex as a new material, which can be suitably used as an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be obtained at high yield by reacting tetrakis(fluoroaryl)borate with a particular kind of ether compound.
In addition, the inventors achieved the present invention when they also discovered that even when tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide containing a coloring component derived from the Grignard reaction and by-product salts, such as magnesium bromide fluoride (MgBrF) produced as a by-product in the Grignard reaction, is used as a raw material, that is, tetrakis(fluoroaryl)borate, a tetrakis(fluoroaryl)boratexe2x80xa2ether complex can be obtained in the form of highly-pure crystals, from which the coloring component and by-product salts can be readily separated/removed.
In other words, a process of producing a tetrakis(fluoroaryl)boratexe2x80xa2ether complex of the present invention relates to a process of producing a tetrakis (fluoroaryl)boratexe2x80xa2ether complex expressed by Formula (4): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R6-R10 represents a fluorine atom, each of R11 and R12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, Y represents a bivalent hydrocarbon group, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkaline earth metal, and is characterized by reacting tetrakis(fluoroaryl)borate expressed by Formula (5): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R6-R10 represents a fluorine atom, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkaline earth metal,
with an ether compound expressed by General Formula (6):
R11xe2x80x94Oxe2x80x94Yxe2x80x94Oxe2x80x94R12xe2x80x83xe2x80x83(6)
where each of R11 and R12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, and Y represents a hydrocarbon bivalent group.
According to the above process, an inexpensive and highly-pure tetrakis(fluoroaryl)boratexe2x80xa2ether complex as a new material suitably used as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be produced at high yield.
Also, according to the above process, even when a raw material, that is, tetrakis(fluoroaryl)borate, contains the impurities, a highly-pure tetrakis (fluoroaryl)boratexe2x80xa2ether complex from which the impurities are removed can be obtained. The tetrakis(fluoroaryl)boratexe2x80xa2ether complex obtained through the above process is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
Further, to fulfill the fourth through seventh objects, the inventors of the present invention conducted an assiduous study. In due course, the inventors achieved the present invention when they discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can be produced efficiently when both a particular kind of tetrakis(fluoroaryl)boratexe2x80xa2ether complex and a compound generating monovalent cationic compounds are used as a starting material.
In other words, to fulfill the above objects, a process of producing the tetrakis(fluoroaryl)borate derivative of the present invention expressed by Formula (2) above is characterized by using both the tetrakis(fluoroaryl)boratexe2x80xa2ether complex expressed by Formula (4) above and a compound generating monovalent cat ionic compounds as a starting material.
According to the above process, since the tetrakis(fluoroaryl)boratexe2x80xa2ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, is used as the starting material, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced efficiently with high purity at low costs.
In addition, to fulfill the above objects, a process of producing tetrakis(fluoroaryl)borate expressed by Formula (5) above is characterized by removing the ether compound expressed by Formula (6) above from the tetrakis(fluoroaryl)boratexe2x80xa2ether complex expressed by Formula (4) above.
According to the above processes, since the tetrakis(fluoroaryl)boratexe2x80xa2ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, is used, highly-pure tetrakis(fluoroaryl)borate can be produced compared with the conventional process of producing tetrakis(fluoroaryl)borate directly from an organic lithium compound or a Grignard reagent.
Further, a process of producing a tetrakis (fluoroaryl)borate derivativexe2x80xa2ether complex of the present invention relates to a process of producing a tetrakis(fluoroaryl)borate derivative-ether complex expressed by General Formula (7): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R-R10 represents a fluorine atom, each of R11 and R12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, Y represents a bivalent hydrocarbon group, Z+ represents a monovalent cationic compound, and n represents 2 or 3, and is characterized by reacting the tetrakis(fluoroaryl) boratexe2x80xa2ether complex expressed by Formula (4) above with a compound generating monovalent cationic compounds.
According to the above process, the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex expressed as General Formula (7) above as a new, useful material for an intermediate in producing the tetrakis(fluoroaryl)borate derivative can be produced.
Further, to fulfill the above objects, a process of producing the tetrakis(fluoroaryl)borate derivative of the present invention expressed by Formula (2) above is characterized by removing the ether compound expressed by Formula (6) above from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex expressed by Formula (7) above.
According to the above process, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex expressed by General Formula (7) above efficiently at low costs.
The purifying process of the tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide of the present invention expressed by General Formula (1) above is a process of applying the treatment with:
{circle around (1)} alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid;
{circle around (2)} an acid;
{circle around (3)} an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or
{circle around (4)} an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid.
Also, the process of producing the tetrakis(fluoroaryl)borate derivative of the present invention expressed by Formula (2) above is a process of reacting a tetrakis(fluoroaryl)borate compound obtained by any of the purifying processes {circle around (1)}-{circle around (4)} with a compound generating monovalent cationic compounds.
Here, the tetrakis(fluoroaryl)borate compound means alkali salts, alkaline earth metal salts, and hydrogen compounds of tetrakis (fluoroaryl)borate. The tetrakis (fluoroaryl) boratexe2x80xa2magnesium halide and tetrakis (fluoroaryl) borate compound are suitable as an intermediate of the tetrakis (fluoroaryl) borate derivative.
Tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide treated in the present invention is a compound, in which each of substituents denoted as R1-R10 is a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 is a fluorine atom and at least one of R6-R10 is a fluorine atom, a substituent denoted as X is a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3.
Examples of the hydrocarbon group include: aryl group, a straight-chain, branched-chain, or cyclic alkyl group having up to 12 carbon atoms, a straight-chain, branched-chain, or cyclic alkenyl group having 2-12 carbon atoms, etc. The hydrocarbon group may further include a functional group that remains inactive to the treatment carried out and reactions taking place in the present invention. Examples of the functional group include: a methoxy group, a methylthio group, an N,N-dimethylamino group, an o-anise group, a p-anise group, a trimethylsilyl group, a dimethyl-t-butyl silyloxy group, a trifluoromethyl group, etc.
The alkoxy group is expressed by General Formula (A):
xe2x80x94ORaxe2x80x83xe2x80x83(A)
where Ra represents a hydrocarbon group. Examples of the hydrocarbon group denoted as Ra in the formula are: an aryl group, a straight-chain, branched-chain, or cyclic alkyl group having up to 12 carbon atoms, a straight-chain, branched-chain, or cyclic alkenyl group having 2-12 carbon atoms. The hydrocarbon group may further include a functional group that remains inactive to the treatment carried out and reactions taking place in the present invention.
Examples of the alkoxy group expressed by General Formula (A) above are: a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a cyclohexyloxy group, an allyloxy group, a phenoxy group, etc.
Of all kinds of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide expressed by General Formula (1) above, the most preferred is tetrakis(pentafluorophenyl)boratexe2x80xa2magnesium bromide.
A process of producing tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide is not especially limited. Tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide can be readily obtained by, for example: i) a process of reacting fluoroaryl magnesium halide as a Grignard reagent with boron halide in the mole ratio of 4:1; ii) a process of reacting fluoroaryl magnesium halide with tris(fluoroaryl)borane in the mole ratio of 1:1; etc. The reaction conditions of the Grignard reaction in these processes are not especially limited.
Tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is obtained in the form of a solution dissolved into a solvent used in the Grignard reaction. Examples of the solvent include, but not limited to:
ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole;
aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;
alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;
aromatic hydrocarbon solvents, such as benzene and toluene; etc.
A mixture of these solvents can be used as well. In case that tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is produced by reacting fluoroaryl magnesium halide with boron halide, magnesium halide, such as magnesium bromide fluoride, produced as a by-product is dissolved into the solution as the impurities.
Examples of the alkali metal salts of carboxylic acid used in the purifying process {circle around (1)} or {circle around (4)} of the present invention include, but not limited to:
alkali metal salts of saturated aliphatic monocarboxylic acid, such as sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, and potassium propionate;
mono- or dialkali metal salts of saturated aliphatic dicarboxylic acid, such as sodium oxalate monobasic, sodium oxalate dibasic, potassium oxalate monobasic, potassium oxalate dibasic, sodium malonate monobasic, sodium malonate dibasic, potassium malonate monobasic, potassium malonate dibasic, sodium succinate monobasic, sodium succinate dibasic, potassium succinate monobasic, and potassium succinate dibasic;
alkali metal salts of unsaturated aliphatic monocarboxylic acid, such as sodium acrylate, potassium acrylate, sodium methacrylate, and potassium methacrylate;
mono- or dialkali metal salts of unsaturated aliphatic dicarboxylic acid, such as sodium maleate monobasic, sodium maleate dibasic, potassium maleate monobasic, potassium maleate dibasic, sodium fumarate monobasic, sodium fumarate dibasic, potassium fumarate monobasic, and potassium fumarate dibasic;
alkali metal salts of aromatic monocarboxylic acid, such as sodium benzoate and potassium benzoate;
mono- or dialkali metal salts of aromatic dicarboxylic acid, such as sodium phthalate monobasic, sodium phthalate dibasic, potassium phthalate monobasic, potassium phthalate dibasic, sodium isophthalate monobasic, sodium isophthalate dibasic, potassium isophthalate monobasic, potassium isophthalate dibasic, sodium terephthalate monobasic, sodium terephthalate dibasic, potassium terephthalate monobasic, and potassium terephthalate dibasic; etc.
Note that, in the present invention, alkali metal salts of carboxylic acid include carbonates, such as lithium carbonate, sodium carbonate, sodium hydrocarbonate, potassium carbonate, and potassium hydrocarbonate.
Examples of the alkali earth metal salts of carboxylic acid used in the purifying process {circle around (1)} or {circle around (4)} of the present invention include, but not limited to:
alkali earth metal salts of saturated aliphatic monocarboxylic acid, such as calcium formate, barium formate, calcium acetate, barium acetate, calcium propionate, and barium propionate;
alkali earth metal salts of saturated aliphatic dicarboxylic acid, such as calcium oxalate, barium oxalate, calcium malonate, barium malonate, calcium succinate, and barium succinate;
alkali earth metal salts of unsaturated aliphatic monocarboxylic acid, such as calcium acrylate, barium acrylate, calcium methacrylate, and barium methacrylate;
alkali earth metal salts of unsaturated aliphatic dicarboxylic acid, such as calcium maleate, barium maleate, calcium fumarate, and barium fumarate;
alkali earth metal salts of aromatic monocarboxylic acid, such as calcium benzoate and barium benzoate;
alkali earth metal salts of aromatic dicarboxylic acid, such as calcium phthalate, barium phthalate, calcium isophthalate, barium isophthalate, calcium terephthalate, and barium terephthalate; etc.
In the present invention, the alkali earth metal salts of carboxylic acid include carbonates, such as calcium carbonate and barium carbonate. Note that, however, in the present invention, the alkali earth metal salts of carboxylic acid do not include magnesium salts of carboxylic acid.
One member or a mixture of two or more members selected from these examples of alkali metal salts of carboxylic acid and alkali earth metal salts of carboxylic acid (hereinafter, collectively referred to as carboxylate) can be used effectively. Of all the example carboxylates, lithium carbonate, sodium carbonate, potassium carbonate, sodium acetate, sodium succinate dibasic, and barium acetate are more preferable than the others. An amount of used carboxylate is not especially limited, but at least one equivalent of the carboxylate to tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide must be used. When a mixture of the alkali metal salts of carboxylic acid and alkali earth metal salts of carboxylic acid is used, a mixing ratio of these metal salts is not especially limited.
Examples of the acid used in the purifying process {circle around (2)}, {circle around (2)}, or {circle around (4)} include, but not limited to:
inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid;
organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid; etc.
One member or a mixture of two or more members selected from these example acids can be used effectively. Of all these example acids, hydrochloric acid, sulfuric acid, formic acid, acetic acid, succinic acid, and malonic acid are more preferable than the others. An amount of used acid is not especially limited, but at least one equivalent of the acid to magnesium used (charged to the reaction series) when producing tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide must be used. In case that a mixture of the inorganic acid and organic acid is used, a mixing ratio of these acids is not especially limited.
Examples of alkali metal hydroxide used in the purifying process {circle around (3)} of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples of alkali earth metal hydroxide used in the purifying process {circle around (3)} of the present invention include calcium hydroxide, barium hydroxide, etc. Note that, however, in the present invention, alkali earth metal hydroxide does not include magnesium hydroxide.
One member or a mixture of two or more members selected from these example alkali metal hydroxides and alkali earth metal hydroxides (hereinafter, collectively referred to as hydroxide) can be used effectively. An amount of used hydroxide is not especially limited, but at least one equivalent of the hydroxide to tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide must be used. In case that a mixture of alkali metal hydroxide and alkali earth metal hydroxide is used, a mixing ratio of these hydroxides is not especially limited.
In case that tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is treated with the carboxylate (purifying process {circle around (1)}), tetrakis(fluoroaryl)boratexe2x80xa2magensium halide is mixed with the carboxylate with stirring. In case that tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is treated with the acid (purifying process {circle around (2)}), tetrakis (fluoroaryl)boratexe2x80xa2magensium halide is mixed with the acid with stirring. In case that tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide is treated with the acid followed by the hydroxide (purifying process {circle around (3)}), after the acid is separated/removed, tetrakis(fluoroaryl)boratexe2x80xa2magensium halide is mixed with the hydroxide with stirring. In case that tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide is treated with the acid followed by the carboxylate (purifying process {circle around (4)}), after the acid is separated/removed, tetrakis(fluoroaryl)boratexe2x80xa2magensium halide is mixed with the carboxylate with stirring.
A method of mixing a solution of tetrakis(fluoroaryl)boratexe2x80xa2magensium halide with the carboxylate, acid, or hydroxide is not especially limited. The carboxylate, acid, or hydroxide may be mixed with a solution of tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide directly (in the form of a solid or a liquid), or optionally, in the form of a solution.
Examples of preferable solvents when using a solution of the carboxylate, acid, or hydroxide include, but not limited to:
water;
ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole;
aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;
alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;
ester solvents, such as methyl acetate and ethyl acetate;
aromatic hydrocarbon solvents, such as benzene and toluene;
alcohol solvents, such as methyl alcohol and ethyl alcohol;
ketone solvents, such as acetone and methyl ethyl ketone; etc.
One member or a mixture of two or more members selected from these example solvents can be used effectively.
A method of mixing tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with the carboxylate, acid, or hydroxide, and a mixing order are not especially limited. , the carboxylate, acid, or hydroxide may be mixed a solution of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide, or the solution of tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide may be mixed with the carboxylate, acid, or hydroxide.
A temperature and a time when mixing the solution of tetrakis (fluoroaryl)boratexe2x80xa2magnesium halide with the carboxylate, acid, or hydroxide with stirring, that is, the treatment conditions, are not especially limited. According to the purifying processes {circle around (1)}-{circle around (4)} of the present invention, the solution of tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide is mixed with the carboxylate, acid, or hydroxide, after which the reaction solution is stirred for a certain time at room temperature, whereby tetrakis (fluoroaryl) boratexe2x80xa2magnesium halide is readily treated. A method of separating/removing the acid when treating tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with the acid followed by the hydroxide or carboxylate is not especially limited. , the acid can be readily separated from a solution of the tetrakis (fluoroaryl)borate compound by a simple manipulation, such as liquid separation (oil-water separation). After the treatment, the tetrakis(fluoroaryl)borate compound is obtained in the form of a solution dissolved into the solvent.
In case that the solution of the tetrakis(fluoroaryl)borate compound contains the carboxylate, acid, or hydroxide, the carboxylate, acid, or hydroxide can be removed optionally by washing or the like. In case that the carboxylate, acid, or hydroxide, or the solution thereof contains the tetrakis (fluoroaryl)borate compound, the tetrakis(fluoroaryl) borate compound can be collected optionally by extraction or the like. Further, in case that the solution of the tetrakis(fluoroaryl)borate compound contains water, water can be removed (dried out) optionally by adding a drying agent, such as magnesium sulfate anhydride.
A tetrakis (fluoroaryl) borate compound expressed by General Formula (3): 
where each of R1-R10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R1-R5 represents a fluorine atom and at least one of R6-R10 represents a fluorine atom, Ma represents a hydrogen atom, alkali metal, or alkaline earth metal, n represents 2 or 3, and m represents 1 when Ma represents a hydrogen atom or alkali metal, or 2 when Ma represents alkaline earth metal, can be obtained by treating tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide through any of the purifying processes {circle around (1)}-{circle around (4)}.
In other words, when tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide is treated with the carboxylate or hydroxide, that is, through the purifying process {circle around (1)}, {circle around (3)} or {circle around (4)}, tetrakis(fluoroaryl)borate expressed by Formula (3) above, in which Ma represents alkali metal or alkaline earth metal, can be obtained. Examples of alkali metal are lithium, sodium, potassium, etc. Examples of alkaline earth metal are calcium, barium, etc.
On the other hand, when tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide is treated with the acid, that is, through the purifying process {circle around (2)}, tetrakis (fluoroaryl)borate expressed by General Formula (3) above, in which Ma represents a, hydrogen atom, can be obtained.
Of all the purifying processes {circle around (1)}-{circle around (4)} of the present invention, the optimum purifying process can be selected depending on the kinds of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide, solvents and the like, so that the resulting tetrakis(fluoroaryl)borate compound is in the desired form (alkali metal salts, alkaline earth metal salts, or hydride), or the post-treatment separatory manipulation, such as liquid separation, can be carried out more readily.
According to any purifying process of the present invention, for example, magnesium halide, which is produced as a by-product while tetrakis (fluoroaryl)boratexe2x80xa2magensium halide is produced through the Grignard reaction, can be converted to either water-soluble or water-insoluble magnesium salts (that is, salts other magnesium hydroxide). Thus, the salts contained in tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide can be separated/removed from the solution of the tetrakis(fluoroaryl)borate compound readily and efficiently through the manipulation, such as liquid separation and filtration. In short, the impurities, such as magnesium halide, can be separated/removed from tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide readily and efficiently. Here, a method of removing/separating the impurities from the solution of the tetrakis (fluoroaryl)borate compound is not especially limited.
When tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide does not contain the impurities, such as magnesium halide, it is preferable to obtain the hydrogen compound, alkali metal salts, or alkaline earth metal salts of tetrakis(fluoroaryl)borate through the above treatment. Because, by applying the above treatment, the reaction with a compound generating monovalent cationic compounds can proceed faster and at higher yield.
As has been explained, the purifying processes of tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide of the present invention are:
{circle around (1)} a process of treating tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with carboxylate;
{circle around (2)} a process of treating tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with an acid;
{circle around (3)} a process of treating tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with an acid followed by the hydroxide; and
{circle around (4)} a process of treating tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide with an acid followed by the carboxylate.
Consequently, it has become possible to provide a purifying process of separating/removing the impurities, such as magnesium halide, from tetrakis(fluoroaryl) boratexe2x80xa2magensium halide readily and efficiently. Also, for example, the reaction of the tetrakis(fluoroaryl) borate compound obtained by the above purifying process with a compound generating monovalent cationic compounds can proceed faster at higher yield. The tetrakis(fluoroaryl) borate compound can be isolated/purified in the form of crystals by removing (distilling out) the solvent optionally.
The compound generating monovalent cationic compounds referred herein (hereinafter, referred to as cationic compound generating compound) can be any compound which generates monovalent cationic compounds in a reaction solvent described below and is reactive with either the tetrakis (fluoroaryl)borate compound or the tetrakis(fluoroaryl) boratexe2x80xa2ether complex or tetrakis(fluoroaryl)borate (the compound will be described below).
Examples of the monovalent cationic compounds generated by the cationic compound seed generating compound include, but not limited to:
ammonium cations, such as n-butyl ammonium, dimethyl ammonium, trimethyl ammonium, triethyl ammonium, triisopropyl ammonium, tri-n-butyl ammonium, tetramethyl ammonium, tetraethyl ammonium, and tetra-n-butyl ammonium;
anilinium cations, such as anilinium, N-methyl anilinium, N,N-dimethyl anilinium, N,N-diethyl anilinium, N,N-diphenyl anilinium, and N,N,N-trimethyl anilinium;
pyridinium cations, such as pyridinium, N-methyl pyridinium, and N-benzyl pyridinium;
quinolinium cations, such as quinolinium and isoquinolinium;
phosphonium cations, such as dimethylphenyl phosphonium, triphenyl phosphonium, tetraethyl phosphonium, and tetraphenyl phosphonium;
sulfonium cations, such as trimethyl sulfonium and triphenyl sulfonium;
iodonium cations, such as diphenyl iodonium and di-4-methoxy phenyl iodonium;
carbenium cations, such as triphenyl carbenium and tri-4-methoxyphenyl carbenium;
monovalent cations of metals other than alkali metal and alkaline earth metal; etc.
Of all these examples, trialkyl ammonium cation, tetraalkyl ammonium cation, dialkyl anlinium cation, alkylpyridinium cation, tetraalkyl phosphonium cation, tetraaryl phosphonium cation, and diaryl iodonium cation are more preferable than the others. Here, anion seeds that form a pair with the monovalent cationic compounds are not especially limited.
Examples of the cation seed generating compound include:
quaternary ammonium compounds, such as tri-n-butylaminexe2x80xa2hydrochloride, N,N-dimethylanilinexe2x80xa2hydrochloride, N,N-dimethylanilinexe2x80xa2sulfate, and tetramethyl ammonium chloride;
nitrogen-containing aromatic heterocyclic compounds, such as pyridine hydrochloride, quinolinexe2x80xa2hydrochloride, N-methyl pyridine iodide, and N-methyl quinoline iodide;
quaternary phosphonium compounds, such as n-butylphosphonium bromide and tetraphenyl phosphonium bromide;
sulfonium compounds, such as trimethyl sulfonium iodide;
iodinium compounds, such as diphenyl iodinium chloride;
carbenium compounds, such as trityl chloride; etc.
, N,N-dimethylanilinexe2x80xa2hydrochloride generates N,N-dimethyl anilinium cations as the monovalent cation seeds. In this case, the anion seeds are chlorine ions.
An amount of used cationic compound generating compound is not especially limited, but at least 0.8 equivalent of cationic compound generating compound to the tetrakis (fluoroaryl) borate compound, a tetrakis (fluoroaryl)boratexe2x80xa2ether complex described below, or tetrakis (fluoroaryl) borate must be used.
The producing process of the tetrakis (fluoroaryl)borate derivative of the present invention uses a reaction solvent. Examples of the reaction solvent include, but not limited to:
water;
ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole;
aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;
alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;
ester solvents, such as methyl acetate and ethyl acetate;
aromatic hydrocarbon solvents, such as benzene and toluene;
alcohol solvents, such as methyl alcohol and ethyl alcohol;
ketone solvents, such as acetone and methyl ethyl ketone; etc.
One member or a mixture of two or more members selected from these example reaction solvents can be used effectively.
In case that the solution of the tetrakis(fluoroaryl)borate compound obtained by the above treatment is used for the reaction, a solvent, in which the tetrakis(fluoroaryl)borate compound is dissolved, can be used as the reaction solvent (either entirely or partially). Thus, in the producing process of the tetrakis(fluoroaryl)borate derivative of the present invention, after tetrakis(fluoroaryl)boratexe2x80xa2magensium halide is treated, the tetrakis(fluoroaryl)borate derivative can be produced from the resulting solution of the tetrakis(fluoroaryl)borate compound without isolating the tetrakis(fluoroaryl)borate compound from the solution.
Exemplary mixing methods of the tetrakis (fluoroaryl)borate compound with the cationic compound generating compound include, but not limited to:
a method of mixing the tetrakis(fluoroaryl)borate compound and cationic compound generating compound with the reaction solvent;
a method of mixing the cationic compound generating compound or a solution thereof with a solution of the tetrakis (fluoroaryl) borate compound;
a method of mixing the tetrakis(fluoroaryl)borate compound or a solution thereof with a solution of the cationic compound generating compound; etc. In case that the solution of the cationic compound generating compound is mixed with the solution of the tetrakis(fluoroaryl)borate compound, and the solution of the tetrakis(fluoroaryl)borate compound is mixed with the solution of the cationic compound generating compound, it is preferable to drop the former to the latter.
A temperature and a time in the reaction of the tetrakis(fluoroaryl)borate compound with the cationic compound generating compound, that is, the reaction conditions, are not especially limited. In the process of the present invention, the reaction can proceed readily by stirring a reaction liquid, prepared by dissolving the tetrakis(fluoroaryl)borate compound and the cationic compound generating compound into the reaction solvent, for a certain time at room temperature. Thus, the object product, that is, the tetrakis(fluoroaryl)borate derivative, can be readily obtained.
For example, when the tetrakis(fluoroaryl)borate compound is the alkali metal salts or alkaline earth metal salts of tetrakis(fluoroaryl)borate and the cationic compound generating compound is N,N-dimethylanilinexe2x80xa2hydrochloride, the object product, that is, N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl)borate can be obtained by reacting the above two compounds with each other, while alkali metal chloride, such as sodium chloride, or alkaline earth metal chloride, such as calcium chloride, is produced as a by-product. The alkali metal chloride or alkaline earth metal chloride can be readily separated/removed from the solution of N,N-dimethyl aniliniumxe2x80xa2tetrakis (fluoroaryl)borate through the manipulation, such as liquid separation, filtration, and washing.
For example, when the tetrakis(fluoroaryl)borate compound is a hydrogen compound of tetrakis(fluoroaryl)borate and the cation seed generating compound is N,N-dimethylaniline hydrochloride, the object product, that is, N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl)borate can be obtained by reacting the above two compounds with each other, while hydrochloric acid is produced as a by-product. The hydrochloric acid can be readily separated/removed from N,N-dimethyl aniliniumxe2x80xa2tetrakis (fluoroaryl) borate through the manipulation, such as liquid separation and washing.
As has been explained, the process of producing the tetrakis(fluoroaryl)borate derivative of the present invention is a process of reacting the tetrakis (fluoroaryl)borate compound obtained by any of the above purifying processes with the cationic compound generating compound.
According to the above process, the tetrakis(fluoroaryl)borate derivative can be produced efficiently at low costs from the tetrakis(fluoroaryl) borate compound, namely, alkali metal salts, alkaline earth metal salts, and hydrogen compound of tetrakis(fluoroaryl)borate. Since the resulting derivative does not contain the impurities, such as magnesium halide, the derivative is so pure that it can be suitably used as a co-catalyst of the metallocene catalyst used in the cationic complex polymerization reaction or a photopolymeric catalyst for silicone.
A producing process of the tetrakis(fluoroaryl) boratexe2x80xa2ether complex of the present invention is a process of reacting tetrakis(fluoroaryl)borate expressed by General Formula (5) above with the ether compound expressed by General Formula (6) above. Consequently, the tetrakis(fluoroaryl)boratexe2x80xa2ether complex of the present invention expressed by General Formula (4) above can be obtained.
Tetrakis (fluoroaryl) borate expressed by General Formula (5) above and used in the above process is a compound, in which each of the substituents denoted as R1-R10 is a hydrogen atom, fluorine atom, a hydrocarbon group or an alkoxy group, provided that at least one of the substituents denoted as R1-R5 is a fluorine atom and at least one of the substituents denoted as R6-R10 is a fluorine atom, a substituent denoted as M is a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n is 2 or 3, and m is 1 when M is a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M is alkaline earth metal. Examples of alkaline-earth metal halide include magnesium chloride, magnesium bromide, magnesium iodide, etc.
In other words, tetrakis(fluoroaryl)borate expressed by General Formula (5) above includes both the tetrakis(fluoroaryl)borate compound expressed by General Formula (3) above and tetrakis(fluoroaryl) boratexe2x80xa2magnesium halide expressed by General Formula (1) above.
Of all the example of tetrakis(fluoroaryl)borate expressed by Formula (5) above, tetrakis (pentafluorophenyl) boratexe2x80xa2magnesium bromide, tetrakis (pentafluorophenyl) boratexe2x80xa2lithium, tetrakis (pentafluorophenyl) boratexe2x80xa2sodium, and tetrakis (pentafluorophenyl) boratexe2x80xa2potassium are particularly preferred. Note that a process of producing tetrakis (fluoroaryl)borate is not limited to the above disclosure.
The ether compound expressed by Formula (6) above and used in the process of the present invention is a compound, in which each of the substituents denoted as R11 and R12 is a hydrocarbon group which may include a substituent containing a hetero atom, and a substituent denoted as Y is a bivalent hydrocarbon group.
Examples of the hydrocarbon group include an alkyl group, an aryl group, a cycloalkyl group, a benzyl group, etc. However, an alkyl group having up to 10 carbon atoms and an aryl group are particularly preferred. Examples of the substituent containing a hetero atom include:
substituents containing oxygen atoms, such as an alkoxy group, an aryloxy group, a cycloalkyloxy group, and an acyloxy group;
substituents containing nitrogen atoms, such as a dialkyl amino group;
substituents containing sulfur atoms, such as an alkylthio group and an arylthio group; etc.
The hydrocarbon bivalent group is preferably a bivalent group selected from the group consisting of an alkylene group having up to six carbon atoms as a carbon chain linking two oxygen atoms, namely, a methylene group possibly having a substituent, an ethylene group possibly having a substituent, a trimethylene group possibly having a substituent, a tetramethylene group possibly having a substituent, a pentamethylene group possibly having a substituent, and a hexamethylene group possibly having a substituent. It is more preferable that the substituent in the bivalent group is an alkyl group having up to six carbon atoms.
Examples of the ether compound expressed by General Formula (6) above (hereinafter, referred to as polyfunctional ether) include:
ethylene glycol dialkyl ether, such as 1,2-dimethoxy ethane, 1,2-diethoxy ethane, ethylene glycol di-n-propyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-sec-butyl ether, ethylene glycol di-t-butyl ether, ethylene glycol dipentyl ether, ethylene glycol dineopentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, and ethylene glycol didecyl ether;
ethylene glycol dicycloalkyl ether, such as ethylene glycol dicyclopropyl ether, ethylene glycol dicyclo butyl ether, ethylene glycol dicyclopentyl ether, ethylene glycol dicyclohexyl ether, ethylene glycol diheptyl ether, ethylene glycol dicyclo octyl ether, ethylene glycol dicyclo nonyl ether, and ethylene glycol dicyclo decyl ether;
unsymetric ethylene glycol methyl alkyl ether, such as ethylene glycol methyl ethyl ether, ethylene glycol methyl isopropyl ether, and ethylene glycol methyl butyl ether;
diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, diethylene glycol dipentyl ether, diethylene glycol dihexyl ether, diethylene glycol diheptyl ether, diethylene glycol dioctyl ether, diethylene glycol dinonyl ether, and diethylene glycol didecyl ether;
triethylene glycol dialkyl ether, such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol diisopropyl ether, triethylene glycol dibutyl ether, triethylene glycol dipentyl ether, triethylene glycol dihexyl ether, triethylene glycol diheptyl ether, triethylene glycol dioctyl ether, triethylene glycol dinonyl ether, and triethylene glycol didecyl ether;
ethylene glycol dialkyl ether having an acyloxy group, such as diethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether methacrylate;
ethylene glycol dialkyl ether having an alkylthio group, such as ethylene glycol, di-2-methylthio ethyl ether;
ethylene glycol dialkyl ether having a dialkyl amino group, such as ethylene glycol di-2-dimethyl amino ethyl ether;
ethylene glycol diaryl ether, such as ethylene glycol diphenyl ether;
diethylene glycol diaryl ether, such as diethylene glycol diphenyl ether;
triethylene glycol diaryl ether, such as triethylene glycol diphenyl ether;
ethylene glycol dibenzyl ether; etc.
It is preferable that the polyfunctional ether is in the state of liquid at room temperature. However, even if the polyfunctional ether is in the state of solid at room temperature, it can be melted into a liquid with heating. Of all these example compounds, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, and diethylene glycol dimethyl ether are particularly preferred because they can be readily converted into highly-pure tetrakis(fluoroaryl)borate through distillation; moreover, they are inexpensive and readily available for industrial use.
The amount of polyfunctional ether used is not especially limited, but it is preferable to use a mole equivalent of polyfunctional ether to tetrakis (fluoroaryl)borate, because tetrakis (fluoroaryl)borate and the polyfunctional ether form the complex when their mole ratio is 1:1 or greater. In the process of producing the tetrakis(fluoroaryl) boratexe2x80xa2ether complex of the present invention, a method of reacting tetrakis(fluoroaryl)borate with the polyfunctional ether is not especially limited, but a method of mixing tetrakis(fluoroaryl)borate with the polyfunctional ether in a solvent is suitable.
The solvent used in the above reaction can be any solvent generally used for organic synthesis, and is not especially limited. Examples of the solvent include: organic solvents, such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and ether solvents; water; etc. One member or a mixture of two or more members selected from these example solvents can be used effectively.
Of all these example solvents, particularly preferred are the solvents with which the solubility of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex is relatively low, namely:
ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole;
aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane;
alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane;
ester solvents, such as methyl acetate and ethyl acetate;
aromatic hydrocarbon solvents, such as benzene and toluene; etc.
When these solvents are used, the tetrakis(fluoroaryl) boratexe2x80xa2ether complex can be readily crystallized and therefore, readily separated from the solution.
When the solvents with which the solubility of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex is high, for example, alcohol solvents, such as methyl alcohol and ethyl alcohol or ketone solvents, such as acetone and methyl ethyl ketone, are used, the tetrakis(fluoroaryl) boratexe2x80xa2ether complex does not crystalize after the formation. Thus, in this case, the solvent is distilled out. Note that polar solvents, such as nitromethane and acetonitrile, are not preferable, because they have higher coordination strength than the polyfunctional ethers and inhibit the formation of the ether complex.
An amount of used solvent is not especially limited, but when the tetrakis(fluoroaryl)boratexe2x80xa2ether complex alone is crystallized and taken out from the reaction series, it is preferable to use the solvent sufficiently, so that tetrakis(fluoroaryl)borate is dissolved therein completely. Consequently, when the complex is formed using tetrakis(fluoroaryl)borate containing a coloring component or by-product salts, the coloring component or by-product salts remain in the reaction series, and for this reason, a highly-pure colorless tetrakis(fluoroaryl) boratexe2x80xa2ether complex can be obtained through the manipulation, such as filtration.
An amount of used solvent does not have to be sufficient to dissolve tetrakis(fluroaryl)borate completely. , the complex can be formed if the reaction takes place in the suspended state. In this case, tetrakis(fluoroaryl)borate is reacted with the polyfunctional ether in the suspended state, and the resulting tetrakis(fluoroaryl)boratexe2x80xa2ether complex is taken out from the reaction series through filtration or the like. In case that the tetrakis(fluoroaryl) boratexe2x80xa2ether complex thus taken out contains the impurities, such as the coloring component and by-product salts, it is preferable to wash the tetrakis (fluoroaryl)boratexe2x80xa2ether complex with an adequate solvent (for example, ether solvents) that can dissolve these impurities. Consequently, a highly-pure colorless tetrakis (fluoroaryl)boratexe2x80xa2ether complex can be obtained.
Alternatively, after the tetrakis(fluoroaryl) boratexe2x80xa2ether complex is formed by reacting tetrakis (fluoroaryl)borate with excessive polyfunctional ether without using the solvent, the excessive polyfunctional ether that does not form the complex may be distilled out. In case that the resulting product contains the impurities, such as the coloring component and by-product salts, it is preferable to wash the resulting product with an adequate solvent (for example, ether solvents) which can dissolve these impurities.
A method of mixing tetrakis(fluoroaryl)borate with the polyfunctional ether and a mixing order thereof are not especially limited. Example mixing methods are: a method of adding the polyfunctional ether to a solution of tetrakis(fluoroaryl)borate; a method of adding a solution of tetrakis(fluoroaryl)borate to the polyfunctional ether; etc.
The reaction temperature is not especially limited, but it is preferably at or below the boiling point of the polyfunctional ether. When the solvent is additionally used, it is further preferable that the reaction temperature is at or below the boiling point of the solvent.
The reaction of tetrakis(fluoroaryl)borate and the polyfunctional ether takes place very fast in a mixed rate-determining manner, but a time is required for the formed complex to grow to crystals. Thus, the reaction time can be set to at least as long as the time necessary for the formed complex to grow to crystals. Further, the reaction can take place under normal, reduced, or applied pressure.
The tetrakis(fluoroaryl)boratexe2x80xa2ether complex can be obtained by the above process. In case that the resulting tetrakis (fluoroaryl) boratexe2x80xa2ether complex contains the impurities, such as the coloring component and by-product salts, the resulting complex can be readily purified to a high level when washed with an adequate solvent (for example, ether solvent) that dissolves these impurities. Hence, the complex can be used as an excellent starting material of the tetrakis (fluoroaryl)borate derivative.
A process of producing the tetrakis(fluoroaryl) borate derivative of the present invention expressed by General Formula (2) above is a process, in which both the tetrakis (fluoroaryl) boratexe2x80xa2ether complex and the aforementioned cationic compound generating compound are used as the starting material. Also, the above process includes a step of removing the polyfunctional ether from the reaction series. In the above producing process, the tetrakis(fluoroaryl)boratexe2x80xa2ether complex or tetrakis (fluoroaryl)borate is reacted with the cationic compound generating compound in the aforementioned reaction solvent.
In other words, a process of producing the tetrakis(fluoroaryl)borate derivative of the present invention includes two types of processes:
a first process, in which, after tetrakis(fluoroaryl)borate is obtained by removing the polyfunctional ether from the tetrakis (fluoroaryl)boratexe2x80xa2ether complex, the resulting tetrakis(fluoroaryl)borate is reacted with the cationic compound generating compound;
a second process, in which, after the tetrakis (fluoroaryl) borate derivative ether complex is obtained by reacting the tetrakis(fluoroaryl)boratexe2x80xa2ether complex with the cationic compound generating compound, the polyfunctional ether is removed from the resulting tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex.
In the first process, it is preferable that a first step of removing the polyfunctional ether from the tetrakis(fluoroaryl)boratexe2x80xa2ether complex is carried out by heating the tetrakis(fluoroaryl) boratexe2x80xa2ether complex in a reaction vessel, so that the polyfunctional ether is distilled out from the reaction vessel.
The heating temperature is not especially limited as long as the polyfunctional ether can be removed from the tetrakis(fluoroaryl)boratexe2x80xa2ether complex. However, a preferable temperature is 40xc2x0 C. or above, and a range between 40xc2x0 C. and 200xc2x0 C. is further preferable. A heating time is not especially limited, either.
To distill out the polyfunctional ether from the reaction vessel, the temperature inside the reaction vessel must be raised higher than the boiling point of the polyfunctional ether under the current pressure inside the reaction vessel. Thus, the pressure inside the reaction vessel may be reduced optionally. Consequently, the polyfunctional ether can be distilled out at a relatively low temperature.
Also, in the first step, the tetrakis(fluoroaryl) boratexe2x80xa2ether complex can be in the form of a solution dissolved into the solvent, or suspended in the solvent.
In the first producing process, if the first step of removing the polyfunctional ether from the tetrakis (fluoroaryl)boratexe2x80xa2ether complex is carried out solely, in other words, if a second step is not carried out, the producing process is same as the producing process of tetrakis(fluoroaryl)borate. According to the above process, inexpensive and highly-pure tetrakis (fluoroaryl)borate can be produced efficiently.
In the first process, the second step of reacting the resulting tetrakis(fluoroaryl)borate with the cationic compound generating compound is carried out in the aforementioned reaction solvent.
In case that the reaction is carried out using a solution of tetrakis(fluoroaryl)borate, a solution in which tetrakis(fluoroaryl)borate is dissolved can be used as the reaction solvent (either entirely or partially). Thus, the tetrakis(fluoroaryl)borate derivative can be produced using the solution of the tetrakis (fluoroaryl)borate obtained in the first step without isolating the compound from the solution.
A method of mixing tetrakis(fluoroaryl)borate with the cationic compound generating compound is not especially limited, and examples of which are: a method of mixing tetrakis(fluoroaryl)borate and the cation seed generating compound with the reaction solvent; a method of mixing the cationic compound generating compound or a solution thereof with a solution of tetrakis(fluoroaryl)borate; a method of mixing tetrakis(fluoroaryl)borate or a solution thereof with a solution of the cationic compound generating compound; etc. In case that the solution of the cationic compound generating compound is mixed with the solution of tetrakis(fluoroaryl)borate, and the solution of tetrakis(fluoroaryl)borate is mixed with the solution of the cationic compound generating compound, it is preferable to drop the former to the latter.
A reaction temperature and a reaction time in the reaction of tetrakis(fluoroaryl)borate and the cationic compound generating compound, that is, the reaction conditions, are not especially limited. In the producing process of the present invention, the reaction is allowed to readily proceed by stirring a reaction liquid, prepared by dissolving tetrakis(fluoroaryl)borate and the cationic compound generating compound into the reaction solvent, for a certain time at room temperature. Consequently, the object product, that is, the tetrakis(fluoroaryl)borate derivative, can be readily obtained.
For example, when the tetrakis(fluoroaryl)borate is alkali metal salts or alkaline earth metal salts of tetrakis(fluoroaryl)borate, and the cationic compound generating compound is N,N-dimethylaniline hydrochloride, the object product, that is, N,N-dimethyl anilinium.tetrakis(fluoroaryl)borate, can be obtained by reacting the above two compounds with each other, while alkali metal chloride, such as sodium chloride, or alkaline earth metal chloride, such as calcium chloride, is produced as a by-product. The alkali metal chloride or alkaline earth metal chloride can be readily separated/removed from the solution of N,N-dimethyl aniliniumxe2x80xa2tetrakis (fluoroaryl) borate through the manipulation, such as liquid separation, filtration, and washing. When the reaction solvent is water, the alkali metal chloride or alkaline earth metal chloride can be readily removed by filtering N,N-dimethyl anilinium.tetrakis (fluoroaryl)borate followed by the washing with water.
Also, for example, when the tetrakis(fluoroaryl) borate is tetrakis(fluoroaryl)boratexe2x80xa2magnesium halide, and the cationic compound generating compound is N,N-dimethylanilinexe2x80xa2hydrochloride, the object product, that is, N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl)borate, can be obtained by reacting the above two compounds with each other, while magnesium halide, such as magnesium bromide chloride, is produced as a by-product.
The magnesium halide can be readily separated/removed from N,N-dimethyl aniliniumxe2x80xa2tetrakis (fluoroaryl)borate through the manipulation, such as liquid separation, filtration, and washing. To be more specific, magnesium bromide chloride can be readily separated/removed by being washed with an acidic aqueous solution, such as hydrochloric acid, or being reacted with N,N-dimethylanilnexe2x80xa2hydrochloride containing excessive hydrochloric acid followed by the washing with water.
In short, the tetrakis(fluoroaryl)borate derivative can be readily isolated/purified as crystals through an optional simple manipulation, such as removal (distillation) of the reaction solvent after a simple manipulation, such as liquid separation and filtration.
In the second Process, a first step of reacting the tetrakis(fluoroaryl)boratexe2x80xa2ether complex with the cationic compound generating compound is carried out in the aforementioned reaction solvent.
A method of mixing the tetrakis(fluoroaryl) boratexe2x80xa2ether complex with the cationic compound generating compound is not especially limited, and examples of which are: a method of mixing the tetrakis(fluoroaryl) boratexe2x80xa2ether complex and the cationic compound generating compound with the reaction solvent; a method of mixing the cationic compound generating compound or a solution thereof with a solution of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex; a method of mixing the tetrakis(fluoroaryl) boratexe2x80xa2ether complex or a solution thereof with a solution of the cationic compound generating compound; etc. In case that the solution of the cationic compound generating compound is mixed with the solution of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex, and the solution of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex is mixed with the solution of the cationic compound generating compound, it is preferable to drop the former to the latter.
A react ion temperature and a reaction time in the reaction of the tetrakis(fluoroaryl)boratexe2x80xa2ether complex and the cationic compound generating compound, that is, the reaction conditions, are not especially limited. In the producing process of the present invention, the reaction is allowed to readily proceed by stirring a reaction liquid made by dissolving or suspending the tetrakis(fluoroaryl)boratexe2x80xa2ether complex and the cationic compound generating compound into the reaction solvent for a certain time at or below the boiling point. Consequently, the object product, that is, the tetrakis(fluoroaryl)borate derivative ether complex, can be readily obtained.
, when the tetrakis(fluoroaryl) boratexe2x80xa2ether complex is a tetrakis(fluoroaryl) boratexe2x80xa2alkali metal salts ether complex or a tetrakis (fluoroaryl)boratexe2x80xa2alkaline earth metal saltsxe2x80xa2ether complex, and the generating compound is N,N-dimethylanilinexe2x80xa2hydrochloride, the object product, that is, N,N-dimethyl aniliniumxe2x80xa2tetrakis (fluoroaryl) boratexe2x80xa2ether complex, can be obtained by reacting the above two compounds with each other, while alkali metal chloride, such as sodium chloride, or alkaline earth metal chloride, such as calcium chloride, is produced as a by-product. The alkali metal chloride or alkaline earth metal chloride can be readily separated/removed from a solution of N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl) boratexe2x80xa2ether complex through the manipulation, such as liquid separation, filtration, and washing. More specifically, the alkali metal chloride can be separated/removed readily by being washed with water.
Also, for example, when the tetrakis(fluoroaryl) boratexe2x80xa2ether complex is tetrakis(fluoroaryl) boratexe2x80xa2magnesium halidexe2x80xa2ether complex, and the cationic compound generating compound is N,N-dimethylanilinexe2x80xa2hydrochloride, the object product, that is, N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl)boratexe2x80xa2ether complex, can be obtained by reacting the above two compounds with each other, while magnesium halide, such as magnesium bromide chloride, is produced as a by-product.
The magnesium halide can be readily separated/removed from the N,N-dimethyl aniliniumxe2x80xa2tetrakis(fluoroaryl)boratexe2x80xa2ether complex through the manipulation, such as liquid separation, filtration, and washing. More specifically, for example, magnesium bromide chloride can be readily separated/removed by being washed with an acidic aqueous solution, such as hydrochloric acid, or being, reacted with N,N-dimethylanilinexe2x80xa2hydrochloride containing excessive hydrochloric acid followed by the washing with water.
In short, the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex can be readily isolated/purified as crystals through an optional simple manipulation, such as removal (distillation) of the reaction solvent or the like after a simple manipulation, such as liquid separation and filtration.
In the second process, if the first step of reacting the und generating compound is carried out solely, in other words, if a second step is not carried out, it is same as the process of the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex. According to the above process, an inexpensive and highly-pure tetrakis (fluoroaryl) borate derivativexe2x80xa2ether complex, which is useful as an intermediate for producing the tetrakis(fluoroaryl)borate derivative, can be produced efficiently.
In the second producing process, it is preferable to carry out the second step of removing the polyfunctional ether from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex by heating the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex within a reaction vessel, so that the polyfunctional ether is distilled out from the reaction vessel.
The heating temperature is not especially limited as long as the polyfunctional ether can be removed from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex. However, a preferable temperature is 40xc2x0 C. or above, and a range between 40xc2x0 C. and 200xc2x0 C. is further preferable. A heating time is not especially limited, either.
To distill out the polyfunctional ether from the reaction vessel, the temperature inside the reaction vessel must be raised higher than the boiling point of the polyfunctional ether under the current pressure inside the reaction vessel. Thus, the pressure inside the reaction vessel may be reduced optionally. Consequently, the polyfunctional ether can be distilled out at a relatively low temperature.
Also, in the second step, the tetrakis(fluoroaryl) borate derivativexe2x80xa2ether complex can be in the form of a solution dissolved into the solvent, or suspended in the solvent.
In case that the reaction is carried out using a solution of the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex, a solution in which tetrakis(fluoroaryl) borate is dissolved can be used as the solvent (either entirely or partially). Thus, the tetrakis(fluoroaryl) borate derivative can be produced using the solution of the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex obtained in the first step without isolating the ether complex from the solution.
In the second producing process, if the second step of removing the polyfunctional ether from the tetrakis(fluoroaryl)borate derivativexe2x80xa2ether complex is carried out solely, in other words, if the first step is not carried out, the producing process is same as the producing process of an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently.
Other and further objects, features, and advantages of the present invention will appear more fully from the following description. Also, the benefits of the present invention will be apparent from the ensuing explanation.
The present invention will be explained in detail by way of examples; however, the present invention is not limited to the following disclosure. In the following examples, NMR (Nuclear Magnetic Resonance) spectrum data are measured using tetramethyl silane (TMS) as a reference reagent in case of 1H-NMR, and using trifluoro acetate as the reference reagent in case of 19F-NMR, by setting the signal of each reference reagent to 0 ppm.